CN107055612B - A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag - Google Patents
A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag Download PDFInfo
- Publication number
- CN107055612B CN107055612B CN201710306634.3A CN201710306634A CN107055612B CN 107055612 B CN107055612 B CN 107055612B CN 201710306634 A CN201710306634 A CN 201710306634A CN 107055612 B CN107055612 B CN 107055612B
- Authority
- CN
- China
- Prior art keywords
- vanadium
- chromium
- chrome green
- reducing slag
- trioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of methods for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag, reducing agent is added after vanadium chromium reducing slag and water slurry, V (IV) in system is reduced into V (III) by the oxidation-reduction potential of adjustment system；Alkali is added into reduction reaction system, alkali leaching process is carried out, the Cr (III) in system is converted to Cr (OH)4 ‑, separation of solid and liquid is then carried out, obtains leachate containing chromium and vanadium trioxide filter cake；Vanadium trioxide filtration cakes torrefaction obtains vanadium trioxide product；To acid adding Precipitation hydrated chromium oxide in leachate containing chromium；Hydrated chromium oxide is through calcining to obtain calcining material；Chrome green product is obtained after the pickling of calcining material, drying.The method of the present invention reducing agent dosage is few, production process will not generate severe toxicity containing hexavalent chromium wastewater and waste residue, the content of V is more than 65.8% in obtained vanadium trioxide；The purity of chrome green is more than 98.2%；Vanadium chromium recovery ratio is high, and the rate of recovery of vanadium is more than 99.1%, and the rate of recovery of chromium is more than 96.1%.
Description
Technical field
The present invention relates to comprehensive utilization of resources and technical field of material, and in particular to a kind of to utilize vanadium chromium reducing slag system
The method of standby vanadium trioxide and chrome green.
Background technology
Vanadium trioxide is the important source material for producing high vanadium ferroalloy and VN alloy.Vanadic anhydride is substituted with vanadium trioxide
High vanadium ferroalloy is produced, the rate of recovery of vanadium can be both improved or the dosage of reducing agent can be saved；And during vanadium nitride is prepared, with three
V 2 O replaces vanadic anhydride, and not only greatling save cost can also avoid what is be also easy to produce from being adhered problem.In addition, three oxidations two
Vanadium can also be directly used in the electronic products such as production thermal element.The raw material for preparing vanadium trioxide at present is mainly five oxidations two
Vanadium, ammonium metavanadate and poly ammonium vanadate, at certain temperature and reducing atmosphere obtained by reaction, reaction temperature is generally higher than 500
DEG C, energy consumption is big, and production cost is high.Chrome green is also important industrial chemicals, is widely used in national defence, electrical alloy, face
Material, hard alloy etc.；Chrome green generally use sodium dichromate is thermally decomposed with ammonium sulfate at present or chromic anhybride thermally decomposes
Prepared by method, production process is both needed to use the hexavalent chromium compound of severe toxicity as raw material.
Vanadium chromium reducing slag is a kind of solid waste that Leaching of Vanadium from Vanadium slag deposition vanadium mother liquid is obtained through restoring neutralisation treatment, in addition to containing
Have outside vanadium and chromium also containing substances such as sodium, silicon, ammonium salts.More than 85% vanadium in vanadium chromium reducing slag exists in the form of V (IV), remaining
In the form of V (III) exist；Chromium is all with Cr (OH)3Form exist.The research on utilization of vanadium chromium reducing slag mainly has two at present
Class：(1) selective oxidation extraction vanadium.Hydrogen peroxide is selected vanadium chromium reducing slag middle or low price vanadium using sodium hydroxide solution for oxidant
Property is oxidized to pentavalent vanadium and realizes the leaching of vanadium, but part Cr (III) also can be by Oxidation Leaching, vanadium chromium inferior separating effect；Vanadium chromium
Alkaline-leaching and vanadium extraction after reducing slag oxidizing roasting, this method need, equipment complexity baked above at 850 DEG C, and obtained after vanadium extraction
Phase structure containing chromium is complicated in containing chromium slag, and chromium is difficult again extraction and application；It under stress can be by vanadium by adding high price vanadic salts
V (III) selective oxidation in chromium reducing slag is V (IV), then utilizes V (IV) and Cr (OH)3PH needed for being reacted with alkali is not
With the leaching V (IV) of selectivity, but due to Cr (OH)3It can also be reacted with alkali and V (IV) reacts the HV generated with alkali2O5 -Advantage
Section is narrow so need stringent control leaching condition and leaching process needs operation with high pressure, of high cost.(2) at the same extract vanadium and
Chromium.Patent CN104357671A, which is disclosed, first uses acid Leaching Vanadium and chromium, then oxidizing lower vanadium and chromium under alkaline condition simultaneously,
Then melamine precipitation, evaporative crystallization extract the technology of sodium chromate, but since the presence of silicon in vanadium chromium reducing slag causes acidleach
Filtering exudate is difficult, and can also be generated largely containing V (V) and Cr (VI) waste water after separating and recovering vanadium chromium from Oxidation Leaching liquid.Specially
Sharp CN106048240A discloses a kind of method of vanadium chromium reducing slag separation and Extraction vanadium chromium, and this method is also first with acid while to leach
The vanadium and chromium of vanadium chromium reducing slag, then again by being selectively oxidized leachate middle or low price vanadium come separation and Extraction vanadium, the party
Method there is also acid leaching liquor separation of solid and liquid it is difficult the problem of, and flow growth process is complicated.In summary as can be seen that vanadium chromium is also at present
The separation and Extraction of vanadium chromium is all that V (IV) and V (III) is utilized to be easier the characteristic that is aoxidized than Cr (III) in former slag, either
Selective oxidation Low Valent Vanadium is V (V) to leaching process selective oxidation Low Valent Vanadium either in leachate, so as to expand vanadium chromium
The difference of matter reaches the purpose of vanadium chromium separation and Extraction, and final products are all the low vanadic anhydrides of added value, whole process flow
It is complicated, of high cost.
Invention content
It is prepared for above-mentioned existing various treatment technologies and vanadium trioxide and chrome green to vanadium chromium reducing slag
Technology there are the defects of, the purpose of the present invention is to provide it is a kind of using vanadium chromium reducing slag to prepare vanadium trioxide and three oxidation two
The method of chromium, it is intended to utilize a kind of vanadium trioxide of solid slag coproduction high added value and chrome green product.
A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag, includes the following steps：
Step (1)：Selective reduction V (IV)：
Reducing agent is added after vanadium chromium reducing slag and water slurry, the oxidation-reduction potential for adjusting system is 0.2V~-0.8V, will
V (IV) in system is reduced into V (III)；
Step (2)：Alkali leaches Cr (III)：
Alkali is added into the reduction reaction system of step (1), carries out alkali leaching process, the Cr (III) in system is converted
Into Cr (OH)4 -, separation of solid and liquid is then carried out, obtains leachate containing chromium and vanadium trioxide filter cake；
Step (3)：It is prepared by vanadium trioxide：
Vanadium trioxide filtration cakes torrefaction obtains vanadium trioxide product；
Step (4)：It is prepared by chrome green：
PH to acid adding regulation and control leachate containing chromium in leachate containing chromium is 9.0~12.0；Precipitation hydrated chromium oxide；Water
Chromium oxide is closed through calcining to obtain calcining material；Chrome green product is obtained after the pickling of calcining material, drying.
The method of the present invention innovatively leaches the collaboration technique of Cr (III), with vanadium chromium using selective reduction V (IV) and alkali
Reducing slag is raw material coproduction vanadium trioxide and chrome green.Using the method for the present invention, realized for the first time with solid slag system
It is standby go out high added value and the vanadium trioxide of high-quality and chrome green product；It is aoxidized compared to existing vanadium trioxide and three
The preparation process of two chromium and the utilization technique of vanadium chromium reducing slag, the present invention have simple for process, at low cost, good product quality,
And vanadium and chromium in vanadium chromium reducing slag can be comprehensively utilized, vanadium chromium recovery ratio is high, and will not generate severe toxicity contains hexavalent chromium wastewater and waste residue,
The characteristics of disclosure satisfy that industrialization production requirements.
Preferably, in step (1), in slurrying process, the solid-to-liquid ratio of vanadium chromium reducing slag and water is 1: 1.5~10g/mL；
Further preferably 1: 3~4g/mL.
Preferably, in step (1), the reducing agent is selected from Na2S2O5、Na2S2O3、Na2S2O4、Na2SO3In one kind or
It is several.
Preferably, in step (1), reduction reaction temperature is 20-110 DEG C, and the time is 1~8 hour.
The inventors discovered that under the reducing agent, regulate and control the oxidation-reduction potential of the system after pulp 0.2V~-
In 0.8V, and it is stirred to react at 20-110 DEG C 1~8 hour；V (IV) in alternative reduction system is V (III)；Have
Good synergy, such as the yield for promoting vanadium trioxide can be cooperateed with.
Further preferably, the oxidation-reduction potential for adding reducing agent adjustment and control system is 0.1V~-0.7V.The study found that
Under the preferred parameter, the recovering effect of separating effect and vanadium chromium is more excellent.
Further preferably, in step (1), reduction reaction temperature is 60-100 DEG C, and the time is 4~6 hours.
In the present invention, the alkali that alkali leaching process uses is alkali metal hydroxide.
Preferably, the alkali is NaOH and/or KOH.
Preferably, in step (2), the dosage of alkali is that Cr (III) is converted to Cr (OH)4 -The 1~6.0 of theoretical amount
Times.
In the present invention, it is stirred to react 0.5~6 hour at being 20-110 DEG C in reaction temperature under the alkali；Selectivity
Leach Cr (III).
Further preferably, in step (2), the dosage of alkali is that Cr (III) is converted to Cr (OH)4 -The 3~4.5 of theoretical amount
Times；Alkali extraction temperature is 70-100 DEG C；It is stirred to react 3~5 hours.The study found that the treatment effect under the preferred scope is more
It is excellent.
The vanadium in vanadium chromium reducing slag is originally made preferentially to be precipitated with vanadium trioxide precipitation form by the present invention program；
It can so ensure that the rate of recovery of vanadium, while additionally aid the highly selective of chromium, high-purity recycling.
Preferably, in step (3), vanadium trioxide filter cake is produced using vacuum drying mode to prepare vanadium trioxide
Product.
Preferably, in step (4), during sour Precipitation, the pH of acid adding regulation and control leachate containing chromium for 9.0~
12.0.The temperature of sour Precipitation process is preferably 25-100 DEG C, the preferred pH and at a temperature of, preferred mixing time
It is 0.5~10 hour.
Further preferably, in step (4), acid out goes out in precipitation process, the pH of acid adding regulation and control leachate containing chromium for 10.0~
11.0.It is stirred 1.5~2.5 hours at 25-70 DEG C again after adjusting pH.The study found that the treatment effect under the preferred scope
It is more excellent.
Preferably, the acid is sulfuric acid, the one or more of hydrochloric acid, phosphoric acid.
Preferably, in step (4), calcination temperature is 800-1300 DEG C, and calcination time is 0.5-6 hours.
Further preferably, in step (4), calcination temperature is 900-1300 DEG C, and calcination time is 3-6 hours.The study found that
Treatment effect under the preferred scope is more excellent；For example, helping that Cr in roasting material (VI) washings is further avoided to be lost in, cause
Handle water pollution.
Most preferably, in step (4), calcination temperature is 1100-1300 DEG C.At the preferred temperature, preferably during calcining
Between be 3-4 hours.
Preferably, in step (4), in acid cleaning process, calcining material is placed in acid solution, the stirring to pulp at 20-100 DEG C
Separation of solid and liquid after 0.5~4h；The acid solution is H+The sulfuric acid or/and hydrochloric acid solution of a concentration of 0.01~2mol/L；Calcining material
Solid-to-liquid ratio with acid solution is 1: 1.5~4g/mL.Under the preferred pickling parameter, treatment effect is more excellent.
The solid drying that separation of solid and liquid after pickling is obtained is to get to the chrome green product of high quality.
A kind of preferred method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag of the present invention, including
Following steps：
Step (a)：After vanadium chromium reducing slag is added water slurry for 1: 1.5~10g/mL by solid-to-liquid ratio, reducing agent adjustment is added in
V (IV) in the oxidation-reduction potential selective reduction vanadium chromium reducing slag of solution is V (III)；Then according in vanadium chromium reducing slag
Chromium by Cr (III) generation Cr (OH)4 -1~6.0 times of addition alkali of theoretical amount, Selectively leaching chromium therein, subsequent solid-liquid point
From obtaining leachate containing chromium and vanadium trioxide filter cake；Vanadium trioxide filter cake is vacuum dried, obtains vanadium trioxide product；
V (IV) in the selective reduction vanadium chromium reducing slag is that V (III) refers to that the oxidation-reduction potential of adjustment system is 0.2V
~-0.8V, and be stirred to react at 20-110 DEG C 1~8 hour；
Step (b)：To acid adding Precipitation hydrated chromium oxide in leachate containing chromium；The Precipitation hydrated chromium oxide refers to
Be control pH of leaching solution containing chromium be 9.0~12.0 to be stirred to react at 25-100 DEG C 0.5~10 hour；
Step (c)：800-1300 DEG C of calcining of hydrated chromium oxide must calcine material in 0.5-6 hours；After calcining material pickling drying
To chrome green product；The calcining material pickling is referred to using H+The sulfuric acid or/and hydrochloric acid of a concentration of 0.01~2mol/L
Solution agitator treating 0.5~4 hour in the case where solid-to-liquid ratio is 20~100 DEG C under conditions of 1: 1.5~4g/mL, then separation of solid and liquid.
Advantageous effect：
In the present invention, the technique created by the present invention using vanadium chromium reducing slag as raw material, it can be achieved that prepare high added value
With the vanadium trioxide of high-quality and chrome green product.
Traditional preparation V2O3Required raw material is all pure pentavalent vanadium compound, and vanadium reverts to trivalent process by pentavalent and needs
A large amount of reducing agent is wanted, and is required for high temperature reduction process, leads to V2O3Manufacturing cost it is high, process is complicated.Similary Cr2O3's
Preparation is also required to high price chromic salts, of high cost, and production process can generate severe toxicity containing hexavalent chromium wastewater and waste residue.Vanadium chromium reducing slag
Belong to dangerous solid waste, but contain vanadium and chromium valuable element again simultaneously.The present invention changes traditional selective oxidation at a low price
Vanadium handles the mode of thinking of vanadium chromium reducing slag, the principle of reduction is more difficult to than V (IV) using Cr (III), by controlling appropriate oxygen
It is V (III) to change the V (IV) in reduction potential selective reduction vanadium chromium reducing slag.Then V is utilized2O3It is not reacted and Cr with alkali
(OH)3Alkaline bleach liquor soluble nature difference realizes the separation of vanadium chromium, and combine water and chromium oxide and impurity be precipitated pH difference and
Hydrated chromium oxide roasting process valence state and composition variation characteristic realize impurity by Selective separation-out hydrated chromium oxide and pickling
It removes, so as to prepare the vanadium trioxide product of high added value and chrome green production as raw material by the use of vanadium chromium reducing slag
Product.
This method reducing agent dosage is few, production process will not generate severe toxicity containing hexavalent chromium wastewater and waste residue, it is simple for process,
At low cost, good product quality added value is high, and the content of V is more than 65.8% in vanadium trioxide；The purity of chrome green is more than
98.2%, it disclosure satisfy that industrialization production requirements.Whole process vanadium chromium recovery ratio is high, and the rate of recovery of vanadium is more than 99.1%, chromium
The rate of recovery is more than 96.1%.
Specific embodiment
Following embodiment is intended to illustrate invention rather than the further restriction to protection scope of the present invention.
Embodiment 1
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to add water slurry by solid-to-liquid ratio 1: 4g/mL, is added in
Na2S2O4Control solution oxide reduction potential is stirred to react 5 hours for -0.5V at 60 DEG C, then according in vanadium chromium reducing slag
Chromium is by Cr (III) generation Cr (OH)4 -3.0 times of theoretical amount add in NaOH, are stirred to react 5 hours at 70 DEG C, separation of solid and liquid must contain
Chromium leachate and vanadium trioxide filter cake.Vanadium trioxide filter cake is washed, vacuum drying, obtains three oxidations containing 65.9%V
Two vanadium products.It adds in sulfuric acid control solution ph into leachate containing chromium to be stirred at room temperature 2.5 hours for 10.0, the water being obtained by filtration
It closes 1300 DEG C of calcinings of chromium oxide and obtains within 3 hours calcining material.Calcining material is using containing H+1mol/L sulfuric acid solutions are in the item of solid-to-liquid ratio 1: 3
The lower 50 DEG C of agitator treatings of part 1 hour obtain the Cr that purity is 98.5% after the solid drying that separation of solid and liquid obtains2O3Product, pickling
It can't detect Cr (VI) in liquid.The rate of recovery of entire technical process vanadium is 99.5%, and the rate of recovery of chromium is 97.5%.
Comparative example 1
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to add water slurry by solid-to-liquid ratio 1: 4g/mL, is added in
Na2S2O4Control solution oxide reduction potential is added at 60 DEG C for 0.25V and is stirred to react 5 hours, then according to vanadium chromium reducing slag
In chromium by Cr (III) generation Cr (OH)4 -3.0 times of theoretical amount add in NaOH, are stirred to react 5 hours at 70 DEG C, separation of solid and liquid
Chromium leachate and filter cake containing vanadium must be contained.Filter cake containing vanadium is washed, vacuum drying, obtains containing barium oxide containing 38.1%V.Xiang Han
It adds in sulfuric acid control solution ph in chromium leachate to be stirred at room temperature 2.5 hours for 10.0, the hydrated chromium oxide 1300 being obtained by filtration
DEG C calcining obtains calcining material for 3 hours.Calcining material is using containing H+The 50 DEG C of stirrings under conditions of solid-to-liquid ratio 1: 3 of 1mol/L sulfuric acid solutions
Washing 1 hour obtains the Cr that purity is 98.0% after the solid drying that separation of solid and liquid obtains2O3Product can't detect in pickle
Cr(VI).The rate of recovery of entire technical process vanadium is 21.6%, and the rate of recovery of chromium is 80.3%.
By comparative example 1 it can be seen that when solution oxide reduction potential not the present invention claims range when, it is impossible to obtain
Qualified vanadium trioxide product, the rate of recovery of vanadium also only have 21.6%；For chromium, product quality slightly lowers, still
The rate of recovery but reduces significantly.
Embodiment 2
The vanadium chromium reducing slag 1000g containing 2.8% vanadium and 9.4% chromium is taken to add water slurry by solid-to-liquid ratio 1: 3g/mL, is added in
Na2SO3Control solution oxide reduction potential is stirred to react 6 hours for 0.1V at 100 DEG C, then according in vanadium chromium reducing slag
Chromium is by Cr (III) generation Cr (OH)4 -3.5 times of theoretical amount add in KOH, are stirred to react 4 hours at 100 DEG C, separation of solid and liquid obtains
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is washed, vacuum drying, obtains three oxygen containing 65.8%V
Change two vanadium products.Hydrochloric acid control solution pH value is added in into leachate containing chromium, 1.5 hours are stirred to react at 70 DEG C for 11.0, mistake
It filters obtained 1100 DEG C of calcinings of hydrated chromium oxide and obtains within 4 hours calcining material, calcining material is using containing H+0.5mol/L hydrochloric acid solutions exist
Washing 1 hour is stirred at room temperature under conditions of solid-to-liquid ratio 1: 2, it is 98.2% to obtain purity after the solid drying obtained after separation of solid and liquid
Cr2O3Product can't detect Cr (VI) in pickle.The rate of recovery of entire technical process vanadium is 99.1%, and the rate of recovery of chromium is
96.1%.
Comparative example 2
The vanadium chromium reducing slag 1000g containing 2.8% vanadium and 9.4% chromium is taken to add water slurry by solid-to-liquid ratio 1: 3g/mL, is added in
Na2SO3Control solution oxide reduction potential is stirred to react 6 hours for 0.1V at 100 DEG C, then according in vanadium chromium reducing slag
Chromium is by Cr (III) generation Cr (OH)4 -3.5 times of theoretical amount add in KOH, are stirred to react 4 hours at 100 DEG C, separation of solid and liquid obtains
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is washed, vacuum drying, obtains three oxygen containing 65.7%V
Change two vanadium products.Hydrochloric acid control solution pH value is added in into leachate containing chromium, 1.5 hours are stirred to react at 70 DEG C for 8.0, mistake
It filters obtained 1100 DEG C of calcinings of hydrated chromium oxide and obtains within 4 hours calcining material, calcining material is using containing H+0.5mol/L hydrochloric acid solutions exist
Washing 1 hour is stirred at room temperature under conditions of solid-to-liquid ratio 1: 2, it is 79.5% to obtain purity after the solid drying obtained after separation of solid and liquid
Cr2O3Product can't detect Cr (VI) in pickle.The rate of recovery of entire technical process vanadium is 99.2%, and the rate of recovery of chromium is
96.2%.
By comparative example 2 it can be seen that when contain acid adding in chromium leachate control solution ph not the present invention claims range
When, it is impossible to obtain qualified Cr2O3Product.
Embodiment 3
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to add water slurry by solid-to-liquid ratio 1: 4g/mL, is added in
Na2S2O4Control solution oxide reduction potential is stirred to react 4 hours for -0.7V at 100 DEG C, then according in vanadium chromium reducing slag
Chromium by Cr (III) generation Cr (OH)4 -4.5 times of theoretical amount add in NaOH, are stirred to react 3 hours at 100 DEG C, separation of solid and liquid obtains
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is washed, vacuum drying, obtains three oxygen containing 66.3%V
Change two vanadium products.Sulfuric acid control solution ph is added in into leachate containing chromium to be stirred at room temperature 2.5 hours for 10.0, is obtained by filtration
900 DEG C of calcinings of hydrated chromium oxide obtain calcining material for 6 hours.Calcining material is using containing H+2mol/L hydrochloric acid solutions are in solid-to-liquid ratio 1: 4
Under the conditions of 50 DEG C of agitator treatings 1 hour, obtain the Cr that purity is 98.3% after the solid drying that separation of solid and liquid obtains2O3Product, acid
It can't detect Cr (VI) in washing lotion.The rate of recovery of entire technical process vanadium is 99.7%, and the rate of recovery of chromium is 97.8%.
Comparative example 3
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to add water slurry by solid-to-liquid ratio 1: 4g/mL, is added in
Na2S2O4Control solution oxide reduction potential is stirred to react 4 hours for -0.7V at 100 DEG C, then according in vanadium chromium reducing slag
Chromium by Cr (III) generation Cr (OH)4 -4.5 times of theoretical amount add in NaOH, are stirred to react 3 hours at 100 DEG C, separation of solid and liquid obtains
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is washed, vacuum drying, obtains three oxygen containing 66.2%V
Change two vanadium products.Sulfuric acid control solution ph is added in into leachate containing chromium to be stirred at room temperature 2.5 hours for 10.0, is obtained by filtration
700 DEG C of calcinings of hydrated chromium oxide obtain calcining material for 6 hours.Calcining material is using containing H+2mol/L hydrochloric acid solutions are in solid-to-liquid ratio 1: 4
Under the conditions of 50 DEG C of agitator treatings 1 hour, obtain the Cr that purity is 98.3% after the solid drying that separation of solid and liquid obtains2O3Product, acid
Cr (VI) content is 0.12g/L in washing lotion.The rate of recovery of entire technical process vanadium is 99.8%, and the rate of recovery of chromium is 96.5%.
By comparative example 3 it can be seen that when hydrated chromium oxide calcination temperature not the present invention claims range when, pickle
In just have Cr (VI), that is to say, that whole process just have containing Cr (VI) waste water generate.
Claims (10)
- A kind of 1. method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag, which is characterized in that including following Step：Step (1)：Selective reduction V (IV)：Reducing agent is added after vanadium chromium reducing slag and water slurry, the oxidation-reduction potential for adjusting system is 0.2V~-0.8V, by system In V (IV) be reduced into V (III)；Step (2)：Alkali leaches Cr (III)：Alkali is added into the reduction reaction system of step (1), alkali leaching process is carried out, the Cr (III) in system is converted to Cr (OH)4 -, separation of solid and liquid is then carried out, obtains leachate containing chromium and vanadium trioxide filter cake；Step (3)：It is prepared by vanadium trioxide：Vanadium trioxide filtration cakes torrefaction obtains vanadium trioxide product；Step (4)：It is prepared by chrome green：PH to acid adding regulation and control leachate containing chromium in leachate containing chromium is 9.0~12.0；Precipitation hydrated chromium oxide；It is hydrated oxygen Change chromium through calcining to obtain calcining material；Chrome green product is obtained after the pickling of calcining material, drying.
- 2. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as described in claim 1, feature It is, in step (1), the oxidation-reduction potential for adding reducing agent adjustment and control system is 0.1V~-0.7V.
- 3. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as described in claim 1, feature It is, in step (1), the reducing agent is selected from Na2S2O5、Na2S2O3、Na2S2O4、Na2SO3One or more of.
- 4. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as described in claim 1, feature It is, in step (1), in slurrying process, the solid-to-liquid ratio of vanadium chromium reducing slag and water is 1: 1.5~10g/mL；Reduction reaction temperature It it is 20-110 DEG C, the time is 1~8 hour.
- 5. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as described in claim 1, feature It is, in step (2), the dosage of alkali is that Cr (III) is converted to Cr (OH)4 -1~6.0 times of theoretical amount；Alkali leaching process Temperature for 20-110 DEG C, the leaching time is 0.5~6 hour.
- 6. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as described in claim 1, feature It is, in step (4), in sour precipitation process, the pH of acid adding regulation and control leachate containing chromium is 10~11.
- 7. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as described in claim 1, feature It is, in step (4), the acid is sulfuric acid, the one or more of hydrochloric acid, phosphoric acid；The temperature of acid out process is 25-100 DEG C, acid It is 0.5~10 hour to analyse mixing time.
- 8. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 7, feature It is, in step (4), calcination temperature is 800-1300 DEG C, and calcination time is 0.5-6 hours.
- 9. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as described in claim 1, feature It is, in step (4), calcination temperature is 1100-1300 DEG C.
- 10. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 9, feature It is, in step (4), in acid cleaning process, calcining material is placed in acid solution, it is solid after 0.5~4h of stirring to pulp at 20-100 DEG C Liquid detaches；The acid solution is the sulfuric acid or/and hydrochloric acid solution of a concentration of 0.01~2mol/L of H+；Calcining material and the solid-liquid of acid solution Than for 1: 1.5~4g/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710306634.3A CN107055612B (en) | 2017-05-04 | 2017-05-04 | A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710306634.3A CN107055612B (en) | 2017-05-04 | 2017-05-04 | A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107055612A CN107055612A (en) | 2017-08-18 |
| CN107055612B true CN107055612B (en) | 2018-06-29 |
Family
ID=59596828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710306634.3A Expired - Fee Related CN107055612B (en) | 2017-05-04 | 2017-05-04 | A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107055612B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892171B (en) * | 2018-07-11 | 2020-10-16 | 首都师范大学 | Thermodynamic reduction method for synthesizing vanadium oxide nano material |
| CN113337715B (en) * | 2021-06-03 | 2022-07-22 | 清华大学 | Method for recycling vanadium and chromium from vanadium and chromium-containing wastewater |
| CN113213537B (en) * | 2021-06-03 | 2022-07-22 | 清华大学 | Method for separating and preparing vanadium trioxide from mixed solution of vanadium and chromium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3677741A (en) * | 1970-08-24 | 1972-07-18 | Monsanto Co | Method of processing ferrophosphorus |
| CN103602819A (en) * | 2013-11-29 | 2014-02-26 | 中南大学 | Comprehensive recovery method of vanadate-chromate-containing solution |
| CN103773956A (en) * | 2012-10-28 | 2014-05-07 | 孙刚 | Method for separating and recycling vanadium and chromium |
| CN106048240A (en) * | 2016-07-15 | 2016-10-26 | 中南大学 | Method for separating and extracting vanadium and chromium from vanadium and chromium reduction slag |
-
2017
- 2017-05-04 CN CN201710306634.3A patent/CN107055612B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3677741A (en) * | 1970-08-24 | 1972-07-18 | Monsanto Co | Method of processing ferrophosphorus |
| CN103773956A (en) * | 2012-10-28 | 2014-05-07 | 孙刚 | Method for separating and recycling vanadium and chromium |
| CN103602819A (en) * | 2013-11-29 | 2014-02-26 | 中南大学 | Comprehensive recovery method of vanadate-chromate-containing solution |
| CN106048240A (en) * | 2016-07-15 | 2016-10-26 | 中南大学 | Method for separating and extracting vanadium and chromium from vanadium and chromium reduction slag |
Non-Patent Citations (1)
| Title |
|---|
| "三氧化二钒的制备工艺及粉体合成研究进展";朱军等;《中国有色冶金 研究开发篇·试验研究 》;20160128(第5期);第77-80页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107055612A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105861829B (en) | A kind of vanadium chromium solution separation, the method for reclaiming vanadium chromium | |
| CN103757425B (en) | A kind of clean process method being produced vanadic acid sodium and chromium acid sodium alkaline liquid by high chrome alum slag | |
| CN103146930B (en) | Method for preparing vanadium oxide | |
| CN109666789B (en) | Method for preparing vanadium pentoxide by using vanadium-chromium slag and manganese carbonate | |
| CN103723765B (en) | Method for preparing titanium dioxide through sulfuric acid method | |
| CN102121068B (en) | Method for preparing vanadium pentoxide | |
| CN103602819B (en) | Comprehensive recovery method of vanadate-chromate-containing solution | |
| CN104388683B (en) | Method for separating and recycling vanadium and chromium from vanadium and chromium-containing material | |
| CN107954474B (en) | Method for producing vanadium product and basic chromium sulfate by using vanadium-chromium solution | |
| CN107055612B (en) | A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag | |
| CN104109758A (en) | Clean process method for extracting vanadium, chromium and iron from vanadium slag step by step | |
| CN106745248B (en) | High-purity sulphuric acid vanadyl solution manufacturing method | |
| CN106987732B (en) | A method of separation and recovery vanadium chromium | |
| CN109055724B (en) | Method for extracting vanadium and chromium from chrome vanadium ore/slag | |
| CN104120271A (en) | Clean production technique of vanadium oxide by vanadium slag carbocholine leaching-hydrogen reduction process | |
| CN110629047B (en) | Method for separating and extracting vanadium and chromium from vanadium and chromium-containing solution | |
| CN109750169A (en) | The method of vanadium chromium is separated from vanadium chromium solution | |
| CN106929696A (en) | TiCl4Refine method of the tailings ammonium soak for high-purity vanadium oxide | |
| CN109399712A (en) | A method of with hydrogen peroxide clean manufacturing high purity vanadic anhydride | |
| CN102167400A (en) | Method for preparing vanadium pentoxide from vanadium-containing solution | |
| CN104386752B (en) | A kind of method that menadione gained raffinate is prepared chromium sulfate basic of producing of utilizing | |
| CN106591587B (en) | A kind of method of containing vanadium and chromium reducing slag selective oxidation alkali leaching separation vanadium chromium | |
| CN106367606B (en) | A method of separating and recovering chromium from vanadium chromium waste residue | |
| CN109336177B (en) | Method for cleanly producing high-purity vanadium pentoxide by using hydrogen peroxide and ammonia water | |
| CN104129814A (en) | Method for producing ammonium metavanadate by using petroleum hydrogenation waste catalyst as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180629 Termination date: 20190504 |